Journal of Mechanical Engineering and Sciences (JMES)

ISSN (Print): 2289-4659; e-ISSN: 2231-8380; Volume 8, pp. 1507-1515, June 2015
Universiti Malaysia Pahang, Malaysia
DOI: http://dx.doi.org/10.15282/jmes.8.2015.25.0147

PURE POLYURETHANE AND CASTOR OIL BASED POLYURETHANE:

SYNTHESIS AND CHARACTERIZATION
M.A. Alaa1, 2, Kamal Yusoh1 and S.F. Hasany1
1

Faculty of Chemical & Natural Resources Engineering,

Universiti Malaysia Pahang, Kuantan Malaysia
2
Department of Chemical Engineering, University of Technology, Baghdad, Iraq
Email: hjkamal@gmail.com; allavip63@yahoo.com
ABSTRACT
In this study, the physico-chemical properties of high performance polyurethane
synthesized from poly propylene glycol (PPG) in comparison with a combination of
PPG and castor oil, is studied using the in-situ polymerization technique. The variations
in properties of both types of polyurethanes are evaluated by Fourier transform infrared
spectroscopy (FTIR), scanning electron microscopy (SEM), X-ray diffraction (XRD)
and the thermogravimetric analysis (TGA) technique. Tensile strength properties were
investigated by film tensile testing equipment. The results indicated the presence of
large -CH stretching in the castor oil mixed polyurethane with a larger oxidative thermal
stability over pure PPG polyurethanes. The tensile properties were found to be almost
comparable in pure and mixed polymers, signifying the usage of mixed polymers in the
future to overcome the environmental and economic crisis in polyurethane synthesis.
Keywords: Castor oil, in-situ polymerization, polyurethanes, vegetable oil, synthesis,
poly propylene glycol.
INTRODUCTION
Polyurethanes (PUs) have been used extensively due to their excellent physical
properties (e.g., low flexibility, high tensile strength, tear and abrasion resistance,
solvent resistance, etc.) and high versatility in chemical structure [1, 2]. PU is generally
synthesized from an isocyanate reaction with polyol. Polypropylene glycol (PPG) is a
polyol basically derived from the petrochemical industry [3]. Due to the high rising
costs of petrochemical feedstock and the enhanced public desire for environmentally
friendly green products, research into the utilization of renewable resources to
manufacture rigid PU is necessary at the present time [4, 5].
PU based on polyols is derived from different vegetable oils, like castor [6-8],
sunflower and rapeseed oils [9]. Castor oil is one of the major natural vegetable oils that
contain a hydroxyl group and so it is widely used in many chemical industries,
especially in the production of PUs [10, 11]. The synthesis of PU nanocomposites is
prepared from natural oil, like castor oil, using HMDI and organically modified clay
and covalently linked PU/n-HMDI composite, which is later collected successfully by
the electro spinning process [6]. The study of the preparation from castor oil exhibited
increasing diisocyanate groups in relation to the polyol amount and increased the
strength at rupture of the obtained polymers and decreased polymer elongation,
resulting in an increasing modulus [12]. A series of 1,4-butane diol chain extended PU
nanocomposites based on castor oil, and 4,40-diphenylmethane diisocyanate (MDI)
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were synthesized with modified clay (Cloisite 30B) as the filler [13]. In this study pure
PU and PUs based on castor oil were synthesized. Then, a comparative study of the
behavioral changes in the physico-chemical properties of the PU made from a mixture
of polyols consisting of PPG and dehydrated castor oil (15%) via in-situ polymerization
was conducted.
EXPERIMENTAL SET-UP
Materials
Commercial grade castor oil was purchased from the local market. It was dehydrated at
80 C in a vacuum oven and characterized for hydroxyl value (148), acid value (2) and
moisture content (0.379%). PPG (Mn=4000) was supplied by SIGMA- Aldrich
Company. The chain extender, 1, 4-butane diol, was procured from Himedia, India. The
toluene diisocyanate (TDI), used as received, was supplied by SIGMA- Aldrich
Company. The catalyst used in this research is DABCO-33LV, a mixture of
triethylenediamine and di (propylene glycol) supplied by Air Products and Chemicals
(United Kingdom).
Synthesis Mechanism
Synthesis Mechanism of Pure PUs
The synthesis mechanism of pure PUs using a pre-polymer technique as shown in
Figure 1, comprises two main steps. First, PPG is reacted with diisocyanate, then
vacuum de-gassed for 5 minutes with high speed stirring for 25 minutes at 75 C to
achieve a homogeneous mixture and generate a pre-polymer with final isocyanate
groups (in this case, polyunsaturated and amorphous). Second, the pre-polymer is
reacted with a chain extender [14] in the presence of a DACO catalyst at high speed
stirring for 1 minute at 75 C to produce viscous PU (in this case, saturated and
crystallized).

Figure 1. Schematic representation of the pure PU synthesis mechanism using the prepolymer technique.
Synthesis Mechanism of Castor-oil-based PUs
The synthesis mechanism of neat COPUs using the pre-polymer technique shown in
Figure 2 comprises two main steps; first, the dehydrated castor oil (15%) is mixed with
the already dehydrated PPG, and second, a polyol mixture of PPG + 15% castor oil is
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reacted with diisocyanate, which was vacuum degassed for 5 minutes with high speed
stirring for 25 minute at 75 C prior to mixing to achieve a homogeneous mixture and
generate a castor-oil-based pre-polymer with final isocyanate groups, followed by
reaction with a chain extender [14] in the presence of a catalyst at high speed stirring for
1 minute at 75 C to produce viscous COPUs (in this case, saturated and crystallized).

Figure 2: Schematic representation of the synthesis mechanism of neat COPUs using the
pre-polymer technique.
Characterization Technique
Fourier transform infrared spectroscopy (FTIR) analysis of PUs was undertaken using a
Vector-22 FT-IR spectrometer (Nicolet 5DX FT-IR) with a resolution of 1 cm-1 from
4000 to 400 cm-1. PU thermal stability (thermogravimetric analysis (TGA)) was tested
using a Universal V4.5A, TA instrument under a nitrogen atmosphere. The crystal
structure of the pure PUs and COPUs was analyzed by X-ray diffraction (XRD), using
an X-ray diffractometer (Rigaku Mini Flex II, Japan) employing a graphite
monochromator and CuK radiation (l nm). Scanning electron microscopy (SEM) was
carried out on a JEOL 6300F machine at an acceleration voltage of 5KV. Tensile testing
of the nanocomposite film was carried out on an instron model 4505 universal testing
machine at 25C, with a load cell of 5 KN and following ASTM D 638. The crosshead
speed was set to 2 mm/min. Samples were cut in a dumbbell shape with an ASTM D
638 (type V).
RESULTS AND DISCUSSION
FTIR Analysis
The micro-domain structures of the pure PU and castor oil based PU were analyzed by
FTIR as shown in Figure 3. A small broad band in the range 40003500 cm-1 was
observed in both samples relating to the O-H stretching vibrations from either water or
hydroxyl terminated compounds, and N-H stretching vibrations from either urea or the
amine group [15, 16]. The CHCH3 peak stretchings are more prominent in the castor
oil based PU, then the pure PU which may be due to
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Pure polyurethane and castor oil based polyurethane: synthesis and characterization

Figure 3. Comparative FTIR spectra for PU (pure PPG & PPG and castor oil)
the larger organic chains present in castor-oil-based PU. Peaks at 1727 cm-1 represent
(C=O) non-bonded urethanes [13], which are likely to be present in larger numbers, in
the castor-oil-based PU synthesis.
TGA Analysis
The result of the TGA (Figure 4) shows the thermal stability of pure PU and castor-oilbased PU under identical conditions and a comparison of the weight losses that
occurred. The thermal stability of these polymers generally starts above 200 C [17]. It
can be seen from Figure 2 that the onset decomposition temperature starts from 250 C
and 235 C for pure PU and castor-oil-based PU, respectively. At 400 C almost 85% of
the pure PU decomposed while the castor-oil-based PUs showed less than 80%
decomposition, which may be due to the different polyol conditions when PPG is mixed
with castor oil which, in turn, may be due to the presence of low hydroxyl content
polyols in the formulation which improved the thermal resistance of the castor-oil-based
PU samples. The overall thermal stability of the PUs showed a slight decreasing trend
as the rigid segments content increased, which is similar to the findings in [17] in which
it was concluded that PU based on vegetable oils has a better oxidative thermal stability
than PU based on PPG [18].

Figure 4. Comparative TGA graph for PU (pure PPG & PPG and castor oil).
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XRD of PU Studies
The XRD patterns of pure PU and COPU are presented in Figure 5. The pure PU X-ray
patterns display the presence of two peaks at 2 = 20.03 (d ang = 4.430 A) and 2 =
28.77 (d ang = 3.10 A) due to the presence of PPG crystals in the soft segments [19].
Meanwhile, pure COPU presence is demonstrated by one peak at 2 = 20.42 (d ang
=4.345) due to the difference in the chemical structure of the soft segment condition,
such as the presence of mono-glyceride and di-glyceride [20]. Moreover, in addition to
the diisocyanate in the castor oil based PUs, the reaction to form the urethane linkage
between the diisocyanate and hydroxyl groups proceeds. This information is presented
in Figure 5 and Table 1.

Figure 5. Comparative XRD graphs for the PUs (pure PPG and PPG and castor oil).
Table 1. XRD data for the pure PUs and COPUs
Samples
Pure PUs
COPUs

d001 []
4.52
4.35
4.38

2 [o]
20.03
28.77
20.59

SEM
In pure PU, during the polymerization reaction, isocyanates reacted with the polyol
gelation, resulting in the formation of the PU cell wall, as shown in Figure 6a. When
castor oil is mixed with PPG as a polyol, the cell wall formation is slower and larger
cells form due to the low reactivity of castor oil [3]. The controlled cell formation is
exhibited by the addition of castor oil in the PPG glycol, as shown in Figure 6b. Due to
the difference in the chemical structure of the soft and hard segments, microphase
separation takes place easily, arising from the incompatibility in the PU [21]. Cells that
are formed can be controlled with the addition of PPG. The addition of PPG to extend
the hard segment is undertaken so that the cell wall is stronger and the formed cell
becomes smaller as compared to the COPU cells.
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Pure polyurethane and castor oil based polyurethane: synthesis and characterization

Figure 6. SEM for PUs (a) without, and (b) with castor oil.
Tensile and Mechanical Properties
Tensile testing was conducted using a tensile universal testing machine. Figures 7 and 8
show the stressstrain and tensile strength curves, respectively, and the effect of castor
oil content. An increase in elongation at the break was observed, while the tensile
strength was found to decrease in comparison with pure PUs. COPUs showed an
improvement of ~21% in elongation at the break (Figure 7) while its tensile strength
decreased to ~35% (Figure 8) when calculated in the comparative stressstrain study of
pure PUs and COPUs with 15 wt% of castor oil. The improved elongation at break of
the COPUs may be due to the presence of CH-CH3 peak stretching that is more
prominent in the COPUs then pure PUs. This may be due to the higher double bonds
and bigger organic chains present in the COPUs [22]. The results show an increase in
the hard segments due to the increase in hydrogen bonding, resulting in more ordered
pure PU molecules. The presence of mono-glyceride in castor oil helps control such a
reaction due to the low reactivity of the secondary hydroxyl group present in the fatty
acid chains [23].

Figure 7. Stressstrain curves for pure COPUs and Pus.

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Figure 8. Tensile strength of pure PUs and COPUs with 0 and 15 wt% of castor oil.
CONCLUSIONS
The results depicted the enhanced physico-chemical properties of the castor-oil-mixed
PUs, over pure PPG originated PUs. The presence of larger organic chains in the castoroil-mixed PUs resulted in a larger oxidative thermal stability over pure PPG PUs. A
slower cell formation was also observed in mixed PUs, exhibiting a controlled
synthesis. Further studies will be undertaken to enhance the mechanical properties by
applying nanofillers. With regard to the mechanical properties, an increase in elongation
at break was observed, while the tensile strength was found to decrease in comparison
with pure PUs. COPUs showed an improvement of ~21% in elongation at break while,
the tensile strength decreased to ~35% when calculated in the comparative stressstrain
study of pure PU and COPU.
ACKNOWLEDGEMENT
Authors are thankful to Universiti Malaysia Pahang, for research grant RDU 130329,
for the financial support.
REFERENCES
[1]

[2]
[3]

[4]
[5]

Lu QW, Macosko CW. Comparing the compatibility of various functionalized

polypropylenes with thermoplastic polyurethane (TPU). Polymer. 2004;45:198191.
Cao X, Lee LJ, Widya T, Macosko C. Polyurethane/clay nanocomposites foams:
processing, structure and properties. Polymer. 2005;46:775-83.
Edhi P, Adityo WH, Eva ON. Effects of chain extender to the structure of castor
oil-based polyurethane foam. International Conference on Chemical and
Material Engineering Grand Candi Hotel, Semarang Indonesia; 2012.
Meier MA, Metzger JO, Schubert US. Plant oil renewable resources as green
alternatives in polymer science. Chemical Society Reviews. 2007;36:1788-802.
Gaidukov S, Cabulis U, Gromilova K, Tupureina V, Grigalovica A. Preparation
and structural properties of free films from rapeseed oil-based rigid
1513

Pure polyurethane and castor oil based polyurethane: synthesis and characterization

[6]

[7]

[8]

[9]
[10]

[11]

[12]

[13]

[14]

[15]

[16]

[17]
[18]
[19]

[20]

[21]

polyurethane-montmorillonite nanocomposites. International Journal of Polymer

Science. 2013; 834595: 1-8.
Pradhan KC, Nayak P. Synthesis and characterization of polyurethane
nanocomposite from castor oil-hexamethylene diisocyanate (HMDI). Adv Appl
Sci Res. 2012;3:3045-52.
Yang LT, Zhao CS, Dai CL, Fu LY, Lin SQ. Thermal and mechanical properties
of polyurethane rigid foam based on epoxidized soybean oil. J Polym Environ.
2012;20:230-6.
Shan CW, Ghazali MI, Idris MI. Improved vibration characteristics of flexible
polyurethane foam via composite formation. International Journal of
Automotive and Mechanical Engineering. 2013;7:1031-42.
Rojek P, Prociak A. Effect of different rapeseedoilbased polyols on mechanical
properties of flexible polyurethane foams. J Appl Polym Sci. 2012;125:2936-45.
Saravari O, Praditvatanakit S. Preparation and properties of urethane alkyd
based on a castor oil/jatropha oil mixture. Progress in Organic Coatings.
2013;76:698-704.
Vashist D, Ahmad M. Statistical Analysis of Diesel Engine Performance for
Castor and Jatropha Biodiesel-Blended Fuel. International Journal of
Automotive and Mechanical Engineering. 2014;10:2155-69.
dos Santos D, Tavares L, Batalha G. Mechanical and physical properties
investigation of polyurethane material obtained from renewable natural source.
Journal of Achievements in Materials and Manufacturing Engineering.
2012;54(2): 211-6.
Kaushik A, Ahuja D, Salwani V. Synthesis and characterization of organically
modified clay/castor oil based chain extended polyurethane nanocomposites.
Composites Part A: Applied Science and Manufacturing. 2011;42:1534-41.
Desantes J, Galindo J, Guardiola C, Dolz V. Air mass flow estimation in
turbocharged diesel engines from in-cylinder pressure measurement.
Experimental Thermal and Fluid Science. 2010;34:37-47.
Cervantes-Uc JM, Cauich-Rodrguez JV, Vzquez-Torres H, Garfias-Mesas LF,
Paul DR. Thermal degradation of commercially available organoclays studied by
TGAFTIR. Thermochimica Acta. 2007;457:92-102.
Cervantes-Uc J, Espinosa JM, Cauich-Rodriguez J, Avila-Ortega A, VazquezTorres H, Marcos-Fernandez A, et al. TGA/FTIR studies of segmented aliphatic
polyurethanes and their nanocomposites prepared with commercial
montmorillonites. Polymer Degradation and Stability. 2009;94:1666-77.
Coutinho FM, Delpech MC. Degradation profile of films cast from aqueous
polyurethane dispersions. Polymer degradation and Stability. 2000;70:49-57.
Javni I, Petrovi ZS, Guo A, Fuller R. Thermal stability of polyurethanes based
on vegetable oils. J Appl Polym Sci. 2000;77:1723-34.
Sahoo NG, Jung YC, So HH, Cho JW. Synthesis of polyurethane
nanocomposites of functionalized carbon nanotubes by in-situ polymerization
methods. Journal of the Korean Physical Society. 2007; 51:S1-6.
Zhang L, Zhang M, Hu L, Zhou Y. Synthesis of rigid polyurethane foams with
castor oil-based flame retardant polyols. Industrial Crops and Products.
2014;52:380-8.
Gao X, Zhou B, Guo Y, Zhu Y, Chen X, Zheng Y, et al. Synthesis and
characterization of well-dispersed polyurethane/CaCO 3 nanocomposites.

1514

Alaa et al. / Journal of Mechanical Engineering and Sciences

[22]

[23]

8(2015)

1507-1515

Colloids and Surfaces A: Physicochemical and Engineering Aspects.

2010;371:1-7.
Choi DS, Zhang Z, Pachauri N. Nanoengineered material applications in
electronics, biology, and energy harnessing. Microelectronics to
Nanoelectronics: Materials, Devices & Manufacturability. 2012:350-69.
Thakur S, Karak N. Castor oil-based hyperbranched polyurethanes as advanced
surface coating materials. Progress in Organic Coatings. 2013;76:157-64.

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